1. A method of making a photo-alignable object comprising topographical surface structures, comprising the steps of:

-providing a feedstock composition comprising a photo-alignable material,

-producing an object (11, 35, 45, 53) having a topographical surface structure from the feedstock composition.

2. A method of making a photo-alignable object, comprising the steps of:

-providing a feedstock composition comprising a photo-alignable material,

-producing an object (11, 22, 24, 35, 44, 45, 53) from the feedstock composition by 3D-printing.

3. A method according to claim 1 or 2, wherein the feedstock composition comprises a photo-alignable material and a further substance which does not comprise a photo-alignable component.

4. A method according to claim 3, wherein the total amount of photo-alignable material in the composition is less than 50% by weight.

5. A method according to claim 3, wherein the photo-alignable material and the further substance are phase separated.

6. The method of claim 3, wherein the photoalignable material comprises a fluorinated moiety.

7. The method of claim 6, wherein the photoalignable material is any of the following polymer structures (i), (ii) or (iii) or a copolymer of 6- [4- [ (E) -3-oxo-3- (4,4, 4-trifluorobutoxy) prop-1-enyl ] phenoxy ] hexyl 2-methylpropyl-2-enoate and 6- [4- [ (E) -3-methoxy-3-oxo-prop-1-enyl ] phenoxy ] hexyl 2-methylpropyl-2-enoate (iv):

8. a method according to any of claims 1-2, wherein the thickness of the object is greater than 500 nm.

9. A method according to any of claims 1-2, wherein the object is curved.

10. A method according to any of claims 1-2, wherein the object is produced on a moving carrier.

11. The method of claim 2, wherein the object has a topographical surface structure.

12. The method according to any one of claims 1 or 11, wherein the relief surface structure comprises a structural element such as a lens, a fresnel lens, a lenticular lens, a lens array, a micro-lens, a prism, a grid or a structure with a rectangular or triangular cross-section.

13. The method of claim 12, wherein the minimum width of the structural elements of the topographical surface structure is greater than 500 nm.

14. The method according to any one of claims 1 or 11, wherein the depth of the relief surface structures is greater than 100 nm.

15. The method according to any of claims 1-2, wherein the photo-alignable object is subsequently exposed to aligning light to form a photo-aligned object.

16. A method according to claim 15, wherein a slave material (13, 23, 56) is applied over at least a portion of the photo-aligned object.

17. The method according to claim 16, wherein the slave material (13, 23, 56) is an LCP material.

18. A photo-alignable object prepared according to any one of claims 1-2.

19. A photo-alignable object prepared according to any one of claims 1-2, having a thickness of more than 2 μm.

20. A photo-alignable object (11, 35, 45, 53) according to any one of claims 1-2, having a topographical surface structure.

21. A photo-alignable object (11, 35, 45, 53) according to claim 20, wherein the depth of the topographical surface structure is greater than 100 nm.

22. A photo-alignable object (11, 35, 45, 53) according to claim 20, wherein the topographical surface structure comprises micro-elements.

23. Photo-aligned object (11, 22, 24, 53) prepared by exposing an object prepared according to any of claims 1-2 to aligning light.

24. Device (10, 20, 58) comprising a slave material (13, 23, 56) which has been aligned by a photo-alignment object (11, 22, 24, 53) according to claim 23.

25. A device (10, 58) according to claim 24, wherein the slave material (13, 56) has at least one surface (12, 54) which is topographically structured and in contact with or over the photo-alignment object (11, 53).

26. A device (58) according to claim 25, wherein the slave material has the function of an anisotropic lens.

27. An autostereoscopic 3D display comprising the device of claim 24.

Background

Recently, photoalignment has been successfully introduced into mass production as follows: liquid Crystal Displays (LCDs) and anisotropic optical films for various applications, such as 3D-switching films, also known as film patterned retarders, for passive 3D televisions and monitors. In each of the above applications, a thin photo-alignment layer is used to align the liquid crystal. If a photoalignment layer is used inside the lc panel to align the switchable liquid crystals, the photoalignment layer must maintain the alignment properties during display, since the liquid crystal material must realign each time it switches due to interaction with an applied electric field. In the case of anisotropic optical films, the liquid crystal crosslinks the liquid crystal after alignment by the photo-alignment layer. For example, a specific embodiment is disclosed in US patent US 6717644. In the case of anisotropic optical films, the liquid crystal crosslinks the liquid crystal after alignment by the photo-alignment layer.

This photo-alignment technique has many advantages compared to conventional alignment of liquid crystals via a brushed surface, such as high reproducibility, alignment patterning and suitability for roll-to-roll preparation. In addition, since the light that generates alignment in the photoalignment layer can be adjusted with surface adjustment, photoalignment can be applied on curved surfaces such as lenses, which is not the case for most other alignment methods. In the state of the art photoalignment technology, a thin layer of photoalignment material is applied to a substrate such as a glass sheet or a plastic foil. Since the alignment information is transferred across the surface of the alignment layer, its thickness is of secondary importance and device manufacturers choose smaller thicknesses to reduce material costs. Typical thicknesses of the photo-alignment layer in the state of the art are about 100nm or less. This is especially the case for LCD alignment layer applications where thicker layers have the disadvantage that they lead to an increase of the effective threshold voltage for switching the LCD.

There are different standard coating techniques that can be used to uniformly apply the photo-alignment layer, as long as the substrate is flat or slightly curved. However, if the photoalignment layer has to be applied to a substrate comprising smaller structures, e.g. microstructures, such as for example micro-lenses or micro-prisms, or structures exhibiting a discontinuous change in shape, such as for example rectangular structures, the application of a thin uniform layer is more complicated and depending on the specific application may even not be achievable.

A further disadvantage of the state of the art photoalignment techniques is that substrates, such as liquid crystals, used as supports for the alignment materials required, first need to be coated with a thin photoalignment layer, which increases the cost and the preparation time and reduces the yield.

Disclosure of Invention

The object of the present invention is to provide a solution that overcomes the above-mentioned drawbacks of the state of the art of photoalignment technology.

The present invention includes methods of making photo-alignable objects. The invention also provides compositions for making photo-alignable objects. Furthermore, the present invention provides various embodiments of photo-alignable objects and devices comprising the same.

In the method according to the invention, the object is prepared from a starting composition comprising a photo-alignable material. The method of the present invention differs from the state of the art photoalignment techniques in that the object itself is photoalignable and no additional deposition of a thin photoalignment layer is required. This has the advantage that the coating steps are reduced, which leads to an increased yield.

Thus, the method of the present invention for making a photo-alignable object comprises the steps of:

-providing a feedstock composition comprising a photo-alignable material

-producing an object from the feedstock composition.

The raw material composition may be the photo-alignable material alone or it may comprise additional substances. Preferably, the feedstock composition comprises at least one photoalignable material and at least one further substance, wherein the feedstock is selected such that there may be a phase separation in an object prepared from the composition such that the concentration of at least one type of photoalignable material is higher at least one surface of the object than in the bulk of the object.

The object referred to in this application may have any form or shape. For example, the object may be an object having a complex surface. In a preferred embodiment, the object is a flexible sheet. In another preferred embodiment, the object comprises topographical surface structures (topographi-cal structures), such as micro-structures like micro-lenses or micro-prisms, or structures showing abrupt shapes, such as rectangular structures.

The object is produced by any suitable method, such as extrusion, casting, moulding, 2D-or 3D-printing or coating.

The present application also relates to the following embodiments:

1. a method of making a photo-alignable object, comprising the steps of:

-providing a feedstock composition comprising a photo-alignable material,

-producing an object (11, 22, 24, 35, 44, 45, 53) from the raw material composition.

2. The method according to embodiment 1, wherein the feedstock composition comprises a photoalignable material and an additional substance that does not comprise a photoalignable moiety.

3. The method according to embodiment 2, wherein the total amount of photo-alignable material in the composition is less than 50% by weight.

4. The method according to any of embodiments 2 or 3, wherein the photo-alignable material and the further substance are phase separated.

5. The method according to any of embodiments 1-4, wherein the photoalignable material comprises a fluorinated moiety.

6. The method according to any one of the preceding embodiments, wherein the object (53) is produced on a carrier (51) and the object is removed from the carrier in a subsequent step.

7. The method according to any one of the preceding embodiments, wherein the object (53) is produced on a support (51) having a topographical surface structure.

8. The method according to any one of the preceding embodiments, wherein the objects (53) are produced on a moving carrier.

9. The method according to any one of the preceding embodiments, wherein a raw material composition (52) comprising a photo-alignable material is poured into a mold (50) providing a surface structure (51) and the object (53) produced from the composition comprising a photo-alignable material is removed from the mold in a later step.

10. The method according to any one of the preceding embodiments, wherein the surface structures (46, 47) are created in the photo-alignable object (45) by embossing with an embossing tool (40) during or after the preparation of the object (45).

11. The method according to any one of the preceding embodiments, wherein the photo-alignable object is subsequently exposed to aligning light.

12. The method according to embodiment 11, wherein a slave material (14, 23, 56) is applied over at least a portion of the photo-aligned object (11, 22, 24, 53).

13. The method according to embodiment 12, wherein the slave material (14, 23, 56) is an LCP material.

14. A photo-alignable object (11, 22, 24, 35, 44, 45, 53) prepared according to any one of embodiments 1-10.

15. A photo-alignable object (11, 22, 24, 35, 44, 45, 53) having a thickness of more than 2 μm.

16. The photoalignable object according to any of embodiments 14 or 15, in the form of a free-standing film (11, 53).

17. A photo-alignable object (11, 35, 45, 53) according to any one of embodiments 14-16, having a topographical surface structure.

18. A photo-alignable object (11, 35, 45, 53) according to embodiment 17, wherein the depth of the topographical surface structure is greater than 100 nm.

19. A photo-alignable object (11, 35, 45, 53) according to embodiment 17 or 18, wherein the surface structure comprises micro-elements.

20. A photo-aligned object (11, 22, 24, 53) prepared by exposing an object according to any one of embodiments 14-19 to aligning light.

21. A device (10, 20, 58) comprising a slave material (13, 23, 56) which has been aligned by a photo-alignment object (11, 22, 24, 53) according to embodiment 20.

22. The device (10, 58) according to embodiment 21, wherein the slave material (13, 56) has at least one surface (12, 54) which is topographically structured and in contact with or over the photo-alignment object (11, 53).

23. The device (58) according to embodiment 22, wherein the slave material has an anisotropic lens function.

24. An autostereoscopic 3D display comprising the device according to any of embodiments 21 to 23.

Drawings

The invention is further illustrated by the accompanying drawings. It is emphasized that the various features are not necessarily drawn to scale.

Fig. 1 depicts a state of the art embodiment of photoalignment, wherein a thin photoalignment layer is applied to a support.

Fig. 2 shows an application in which a photo-alignable object with a surface structure has been used to align a slave material on top.

FIG. 3 shows a liquid crystal cell in which the liquid crystal is aligned by two photo-aligned objects.

FIG. 4 illustrates an example of producing a photo-alignable object having a surface structure.

Fig. 5 illustrates a method of producing a photo-alignable object with a surface structure by imprinting.

Fig. 6 shows a method of producing an optically anisotropic lens using a photo-aligned object having a surface structure.

Detailed Description

According to a first aspect of the present invention, there is provided a method of preparing a photo-alignable object.

A photo-alignable object in the context of the present application means an object comprising a photo-alignable material.

The method for preparing the photo-alignable object comprises the following steps:

-providing a feedstock composition comprising a photo-alignable material

-producing an object from the feedstock composition.

The object according to the invention may have any form. For example, the object may have a form of a sphere, cube, cylinder, tube, sleeve, sheet, lens, ellipsoid, cuboid, torus, cone, wedge, pyramid, or prism. The object may be flat or curved, rigid or flexible. Although the above examples of objects are merely basic geometric forms, chosen to illustrate the scope, the term "object" shall include any other object that may have more complex shapes and surfaces.

The object may be, for example, a free-standing film. The free-standing film may be prepared directly, for example by extrusion, or the object made from the feedstock composition may be produced as a film on a support, which in a further step is detached from the support.

To characterize the dimensions of the object according to the invention, the thickness of the object should be interpreted as the maximum thickness in the thickness direction of the object. The thickness direction should be the direction of the smallest dimension of the object. For example, in the case of a sheet, the thickness direction is perpendicular to the sheet surface. In case the object has a topographical surface structure in the thickness direction, the thickness should be measured up to the top of the structure, as indicated by the thickness d of the object 11 in fig. 2.

The object according to the invention has a thickness of more than 200 nm. Preferably, the object thickness is greater than 500nm, more preferably greater than 2 μm and most preferably greater than 10 μm. For some applications, for example, if the object is not intended to be on a support during or after its preparation, the object thickness is preferably greater than 50 μm, more preferably greater than 200 μm and most preferably greater than 1 mm.

In the context of the present application, a "photo-alignable material" is a material that induces anisotropic properties upon exposure to aligning light. Similarly, a "photo-alignable object" is an object that induces anisotropic properties upon exposure to aligning light. In addition, the terms "photoalignment material" and "photoalignment object" are used to refer to photoalignment material and photoalignment objects that have been aligned by exposure to alignment light.

In the context of the present invention, the term "aligned light" means light which can induce anisotropy in the photo-alignable material as well as at least a part of its linear or elliptical polarization and/or which is incident from an oblique direction to the surface of the photo-alignable material. Preferably, the alignment light is linearly polarized with a degree of polarization greater than 5: 1. The choice of wavelength, intensity and energy of the alignment light depends on the photosensitivity of the photo-alignable material. Typically, the wavelength is in the UV-A, UV-B and/or UV-C range or in the visible range. Preferably, the alignment light comprises light having a wavelength of less than 450 nm. More preferably, the alignment light comprises light having a wavelength of less than 420 nm.

If the alignment light is linearly polarized, the polarization plane of the alignment light means a plane defined by the propagation direction and the polarization direction of the alignment light. In the case where the alignment light is elliptically polarized, the polarization plane of the alignment light means a plane defined by the propagation direction of the light and by the major axis of the polarization ellipse.

The terms "anisotropic" and "anisotropy" may refer to, for example, optical absorption, birefringence, electrical conductivity, molecular alignment, alignment properties for other materials, such as liquid crystals, or mechanical properties, such as elastic modulus. The term "alignment direction" in the context of the present application shall refer to the symmetry axis of the anisotropic properties.

The production of the object from a starting composition comprising a photo-alignable material may be achieved by any suitable method, such as casting, moulding including injection moulding and pressure moulding, or extrusion, 2D-or 3D-printing and coating. Suitable coating methods are, for example, spin coating, knife coating, contact roll coating, cast coating, slot coating, calender coating, die coating, dipping, brushing, casting with a rod (casting with a bar), roll coating, flow-coating, wire coating, spraying, dipping, spin coating, cascade coating, curtain coating, air knife coating, gap coating, rotary screen, reverse roll coating, gravure coating, metering rod (Meyer bar) coating, slot die (extrusion) coating, hot melt coating, roll coating, flexo coating. Suitable printing methods include: screen printing, relief printing such as offset printing, ink jet printing, intaglio printing such as direct gravure or rotogravure, lithography such as offset printing, or engraving such as screen printing.

The object may be prepared by depositing a starting composition comprising the photo-alignable material on a support, which may be flat or any form of mold.

The support may be rigid or flexible. In principle it can consist of any material. Preferably, the carrier comprises plastic, glass or metal or is a silicon wafer. If the support is flexible, it is preferred that the support is a plastic or a metal foil. Preferably, the surface of the support on which the feedstock composition is deposited has a topographical surface structure. Topographical surface structures are, for example, lenses, such as fresnel and biconvex lenses, and lens arrays, including microlenses; prisms, including microprisms; grids and structures with rectangular or triangular cross-sections. The structure may be cyclic or acyclic.

The support may be moved during deposition of the feedstock composition comprising the photo-alignable material. For example, the body of the feedstock composition may be produced by depositing the feedstock composition on a moving flexible sheet, preferably plastic or metal, by a rolling process in a continuous roll. The resulting film may be wound onto a roll along with the carrier sheet or the object may be removed from the carrier and then wound as a free-standing, unsupported film.

A photo-alignable object of fixed cross-sectional profile can be produced by an extrusion process rather than depositing the feedstock composition on a support. The object produced by extrusion may be, for example, a flat or tubular film. The object is cut in the length direction or wound on a roll.

Preferred methods of the present invention further comprise the step of creating a surface structure in the photo-alignable object. Typical structures are, for example, lenses such as fresnel and biconvex lenses and lens arrays, including microlenses; prisms, including microprisms; grids and structures with rectangular or triangular cross-sections. The structure exemplified as described above should also include an inverted structure profile, which is especially applied if the structure needs to be replicated into another material. The structure may be cyclic or acyclic. The term structural element shall refer to the smallest structural element that can characterize the structure. For example, if the structure comprises a microlens, such as a microlens array, then the structural element is a microlens. In the case of a cyclic structure, the structural elements are periodically repeating units. The azimuthal dimension (azimuthal dimension) of the structural elements may cover the range of 100nm up to the size of the object. Preferably, the minimum width of the structural element according to the invention is more than 500nm, more preferably more than 5 μm and most preferably more than 50 μm. The structure depth may be 10nm to several centimeters. Preferably, the depth of the structure is greater than 100nm, more preferably greater than 1 μm and most preferably greater than 10 μm.

In a preferred method of the invention for producing a photo-alignable object with a surface structure, the starting composition comprising a photo-alignable material is cast into a mold providing the corresponding structure, and the object produced from the composition comprising a photo-alignable material is removed from the mold in a subsequent step.

In another preferred method of producing a photo-alignable object with a surface structure according to the invention, the structure is embossed into the surface of the photo-alignable object during or after the preparation of the object using an embossing tool providing the corresponding structure.

Further methods of producing the surface structure are photolithography and etching using the raw materials, laser ablation, self-organization of the materials or deposition of the raw material composition in the desired form, for example by printing methods such as inkjet printing or 3D printing.

In order to create anisotropy in any of the photo-aligned objects described above, the method may comprise the steps of: exposing the photo-alignable object to aligning light to convert the photo-alignable object to a photo-aligned object.

In a preferred variant of the method described above, the slave material is applied on the surface of the photoalignment object. Preferably, the slave material is a Liquid Crystal Polymer (LCP) material. The slave material may be applied by coating and/or printing with or without a solvent and may be applied over the entire area of the object or over only a portion thereof. The slave material should cover at least a portion of the object without having to be applied over its entire area. Preferably, the method comprises heating the slave material before or after it is applied to the object. The method may also include initiating polymerization in the slave material by heat treatment or exposure to actinic light. Depending on the nature of the slave material, polymerization may be facilitated under an inert atmosphere such as nitrogen, or under vacuum. The slave material may comprise isotropic or anisotropic dyes and/or fluorescent dyes.

In the context of this application, "slave material" refers to any material that has the ability to create anisotropy upon contact with a photoalignment material. The properties of the anisotropy in the photo-alignment material and in the slave material may differ from each other. For example, the slave material may exhibit optical absorption anisotropy for visible light and may therefore act as a polarizer, while the anisotropy of the photoalignment material may be related only to this molecular orientation. The photo-alignable material component may also be present, for example, in a copolymer, which is not sensitive to alignment light, but which undergoes a photoreaction upon exposure to alignment light due to interaction with the photosensitive component to produce anisotropic properties. The above materials exhibit the properties of the photo-alignable material as well as the properties of the secondary materials, but should be included within the meaning of photo-alignable materials.

The slave material may comprise a polymerizable and/or non-polymerizable compound. Within the context of the present application, the terms "polymerizable" and "polymerized" include the meanings "crosslinkable" and "crosslinked", respectively. Likewise, "polymerizing" includes meaning "crosslinking".

Preferably, the slave material is a self-organizing material. More preferably in that the slave material is a liquid crystal material and even more preferably in that the slave material is a liquid crystal polymer material.

Liquid Crystal Polymer (LCP) material as used within the context of the present application means a liquid crystal material comprising liquid crystal monomers and/or liquid crystal oligomers and/or liquid crystal polymers and/or cross-linked liquid crystals. In case the liquid crystal material comprises liquid crystal monomers, said monomers may be polymerized, typically after creating anisotropy in the LCP material due to contact with the photo-alignment material. The polymerization may be initiated by heat treatment or by exposure to actinic light, preferably comprising ultraviolet light. The LCP material may be composed of a single class of liquid crystal compounds, but may also be a combination of various polymerizable and/or non-polymerizable compounds, wherein not all of the compounds need to be liquid crystal compounds. Furthermore, the LCP material may contain additives, for example, photoinitiators or isotropic or anisotropic fluorescent and/or non-fluorescent dyes.

In accordance with a second aspect of the present invention, a photo-alignable object is provided.

The object may have any form; it may be in the form of a flexible sheet, but may be any kind of shape that is rigid. The object may be part of a device, for example as a layer in a stack of various material layers, which may be produced sequentially.

The anisotropy is created in the photo-alignable objects by exposing them to aligning light. The anisotropy induced in the photo-alignable object may be further transferred to a secondary material to contact the surface of the object, such as by printing, coating or casting methods, including, but not limited to: spin coating, knife coating, doctor blade coating, contact injection coating, cast coating, slot coating, calendar coating, die coating, dipping, brushing, casting with rods (casting with a bar), roller coating, flow-coating, injection molding, wire coating, spray coating, dip coating, spin coating, cascade coating, curtain coating, air knife coating, gap coating, rotary screen, reverse roll coating, gravure coating, metering rod (Meyer bar) coating, slot die (extrusion) coating, hot melt coating, roller coating, flexographic coating, screen printing machines, relief printing such as offset printing, ink jet printing, 3D-printing, intaglio printing such as direct gravure printing or offset gravure printing, lithographic printing such as offset printing, or engraved printing such as screen printing.

Preferred applications include use as alignment surfaces for switchable liquid crystals in LCDs and as slave materials, for example for the preparation of optical retarders or polarizing films, which may contain orientation patterns.

In a preferred embodiment of the invention, the photo-alignable object has a topographical surface structure. The structure may comprise a micro-element or an array of micro-elements. Typical structures are, for example, lenses such as fresnel and biconvex lenses and lens arrays, including microlenses; prisms, including microprisms; grids and structures with rectangular or triangular cross-sections. The structure may be cyclic or acyclic. The structure exemplified as described above should also include an inverted structure profile, which is especially applied if the structure needs to be replicated into another material. The azimuthal dimension (azimuthal dimension) of the structural elements may cover the range of 100nm up to the size of the object. Preferably, the minimum width of the structural element according to the invention is more than 500nm, more preferably more than 5 μm and most preferably more than 50 μm. The structure depth may be in the range of 10nm to several centimeters. Preferably, the depth of the structure is greater than 100nm, more preferably greater than 1 μm and most preferably greater than 10 μm.

Photoalignable objects with topographic surface structures may be photoaligned similar to those of the state of the art and may be used to align slave materials, such as switchable liquid crystals in LCD or LCP materials, the latter allowing for the fabrication of optical retarders or polarizers. The slave material boundary on the object side will also be topographically structured, since the surface structure of the object will form into the slave material. Thus, the optical properties of the slave material are spatially adjusted in accordance with the surface structure. Typical structures so replicated are, for example, lenses, such as fresnel and lenticular lenses, and lens arrays, including microlenses; prisms, including microprisms; grids and structures with rectangular or triangular cross-sections. The structure may be cyclic or acyclic. This can give new applications for optical elements, such as optically anisotropic lenses for use in autostereoscopic 3D displays, as part of a system for switching between 2D and 3D modes. Other applications include brightness enhancement films for LCDs, optically coupled arrays for LCDs and Organic Light Emitting Devices (OLEDs), for displays or lighting and optical security elements.

Fig. 1 shows an embodiment of the device, which is based on the state of the art photoalignment. In this technique the photoalignable material is deposited as a thin layer 2 on a substrate 1. Once the photo-alignable material layer is exposed to aligning light, alignment capability is created in this layer. After coating the liquid crystal layer 3 on top of the photo-alignment material, the liquid crystal material is uniformly aligned according to the direction 4 defined by the alignment light.

In the embodiment of fig. 2, the device 10 is based on a photo-alignable object 11 according to the invention, which comprises a surface structure 12. Upon exposure of the photo-alignable object to aligning light, an alignment capability is created at the surface of the object structure. After coating the liquid crystal layer 13 on top of the photo-alignment material, the liquid crystal material is aligned evenly according to a direction 14 defined by the alignment light.

In accordance with a third aspect of the present invention, there is provided a device comprising a photo-alignment object.

The device according to the invention comprises a slave material which has been aligned by a photo-alignment object. The slave material is removed from the photo-aligned object after alignment has been established among the slave materials. Preferably, the slave material is an LCP material. The device is preferably transparent to visible light, having a light transmission higher than 60%, more preferably higher than 80%. The slave material may comprise isotropic or anisotropic dyes and/or fluorescent dyes. Preferred devices according to the present invention also comprise metallic or non-metallic reflectors. The device preferably comprises one or more layers for protecting the device from mechanical or electromagnetic influences.

In a preferred embodiment according to the invention, the slave material has at least one relief-structured surface and is in contact with or has been in contact with the photo-alignment object. Typical topographical surface structures are, for example, lenses, such as fresnel and biconvex lenses and lens arrays, including microlenses; prisms, including microprisms; grids and structures with rectangular or triangular cross-sections. The structure may be cyclic or acyclic. Preferably, the structure of the relief supports light focusing.

For example, FIG. 6 illustrates a method of making an optically anisotropic lenticular lens. Fig. 6a shows a mold 50 which provides the required surface profile 51 of a lenticular lens. In principle any material, such as metal or polymer, can be used for the mould. A feedstock composition 52 comprising a photo-alignable material is deposited in the mold by a suitable method, such as casting (fig. 6 b). Depending on the kind of the raw material composition 52, a heating and/or ultraviolet-curing step may be applied to cure it. The resulting photo-alignable object 53 may then be removed from the mold. As shown in fig. 6c, the resulting photo-alignable object 53 has a surface profile 54 that is the inverse of the surface profile of the lenticular lens array, since the surface structure of the mold has been replicated into the object 53. The photo-alignable object 53 is then exposed to alignment light to convert it into a photo-aligned object, the alignment direction being indicated by arrow 55. Subsequently, LCP material is deposited on the photo-aligned object 53, so that it fills the surface structures 54, as shown in fig. 6 d. Depending on the LCP material properties, thermal treatment and/or uv curing may be required to align the liquid crystal molecules and to cure the LCP. The resulting LCP layer is in the form of a lenticular lens array 56. The alignment direction 57 of the liquid crystal molecules is parallel to the alignment direction 55 generated in the photo-alignment object 53. The optical properties of the object 53 and the optical properties of the LCP material may be selected such that the lenticular lenses 56 and the object 53 together form an optical device 58. Because the liquid crystal molecules are uniaxially aligned, the LCP layer is birefringent. The refractive index of the LCP along the alignment direction corresponds to the extraordinary refractive index (extraordinary index) n_eAnd the refractive index perpendicular to the alignment direction corresponds to a common refractive index (index) n_o. According to a preferred embodiment of the invention, the selection object 53 is foldedIndex of refraction of about two indices of refraction n_eAnd n_oOne of them is the same. If, for example, the refractive index of the object is equal to the ordinary refractive index n of the LCP layer_oEqual and therefore of extraordinary refractive index n_eIn contrast, the optical properties of device 58 with respect to polarized light depend on the polarization direction of the light. For polarized light with a polarization direction parallel to the orientation direction 57, there is a refractive index step at the boundary between the object 55 and the LCP material. Thus, device 58 operates similar to a lenticular lens array in accordance with the geometry and associated refractive index. However, for polarized light with a polarization direction perpendicular to the orientation direction 57, there is no refractive index difference at the boundary between the object 55 and the LCP material and the light is not refracted. Thus, the lens array is active or inactive depending on the light polarization direction. In combination with additional optical elements that can rotate the plane of polarization of light by 90, such as liquid crystal cells, the lens array device 58 can be switched between active and inactive.

In a preferred embodiment, the device comprises an optically anisotropic lens.

For example, the device according to the invention may be used in an autostereoscopic 3D display as part of a system for converting between 2D and 3D modes. Other applications include brightness enhancement films for LCDs, and light out-coupling arrays for Organic Light Emitting Devices (OLEDs), such as display or OLED lighting applications. Other devices according to the present invention may be used as part of an LCD backlight unit. Preferably, the device according to the invention is used for an optical security element.

In accordance with a fourth aspect of the present invention, there is provided a composition for preparing a photo-alignable object.

The feedstock composition comprising a photo-alignable material may comprise more than one type of photo-alignable material.

The feedstock composition comprising a photoalignable material may comprise additional substances that do not comprise a photoalignable component. Such materials include polymers, dendrimers, oligomers, prepolymers, and monomers, which polymerize during or after fabrication of the object. Examples of suitable polymer classes are, but are not limited to: polyalkylene, such as polyethylene, polypropylene, polycycloolefin COP/COC, polybutadiene, poly (meth) acrylate, polyester, polystyrene, polyamide, polyether, polyurethane, polyimide, polyamic acid, polycarbonate, polyvinyl alcohol, polyvinyl chloride, cellulose, and cellulose derivatives such as cellulose triacetate. Examples of suitable monomer classes are: mono-and polyfunctional (meth) acrylates, epoxides, isocyanates, allyl derivatives and vinyl ethers.

Preferably, the photo-alignable object according to the invention does not have a liquid crystal phase above 20 ℃, more preferably it does not have a liquid crystal phase above 10 ℃. The reason is that those liquid crystals are aligned by self-organization, generally in a small number of domains. Photoalignment will compete with random liquid crystal alignment and require long exposure to polarized uv light and/or heating of the object to temperatures above the clearing temperature of the liquid crystal material to perform the photoalignment process in the isotropic phase of the material, where the liquid crystals are out of order. This would complicate the alignment process anyway. In accordance with the above, it is preferred that the starting material composition comprising the photo-alignable material, without any solvent that needs to be removed after formation of the object, does not have a liquid crystalline phase above 20 ℃, more preferably not more than 10 ℃. On the other hand, it is preferred that the individual substances in the raw material composition comprising the photo-alignable material do not exhibit a liquid crystal phase above 20 ℃, more preferably not more than 10 ℃.

The term substance to which the raw material composition comprising the photo-alignable material relates shall not include a solvent which is used for preparing the composition and the object and which is later removed, e.g. by drying. In other words, the term substance includes only those compounds that remain in the final object.

In particular, the feedstock composition comprising the photoalignable material may comprise additives for improving adhesion.

Furthermore, the raw material composition comprising the photo-alignable material may comprise isotropic or anisotropic dyes and/or fluorescent dyes.

Depending on the type of starting material in the composition, phase separation may occur between the photo-alignable material and other substances. By appropriate selection of the raw material composition, the phase separation can be controlled such that upon preparation of the object, a substantial portion of the photo-alignable material separates to the surface of the object. This further allows for a reduction in the amount of photoalignable material in the composition. Preferably, the total amount of photo-alignable material in the composition is less than 50%, more preferably less than 20% and most preferably less than 10% by weight. The amount of photoalignable material may be less than 1 wt% or even less than 0.1 wt%, depending on the thickness of the object prepared from the feedstock composition. In very individual cases 0.01 wt% of photo-alignable material is still sufficient to obtain sufficient alignment properties. Preferably, the photoalignable material comprises a fluorinated and/or siloxane moiety and/or is a polysiloxane to aid phase separation.

In a preferred embodiment, the composition according to the invention comprises a photoalignable material and a further substance, which may or may not be photoalignable. Both the photo-alignable material and the further substance may be polymers, dendrimers, oligomers, pre-polymers or monomers. The photo-alignable material and the other species are selected such that the monomer dipole moments of the photo-alignable material and the other species are different from each other. The monomer dipole moment refers to the monomer dipole moment or, in the case of polymers, oligomers and prepolymers, to the dipole moment of the monomer units of the above-mentioned polymers, oligomers and prepolymers, respectively. Preferably, the difference in dipole moment of the monomers is more than 0.5 debye, more preferably more than 1 debye and most preferably more than 1.5 debye. The composition may comprise additional photoalignable or non-photoalignable substances.

The photo-alignable material in the composition for preparing the object according to the invention may be any kind of photosensitive material in which anisotropic properties may be generated upon exposure to aligning light, irrespective of the photo-reaction mechanism. Thus, suitable photo-alignable materials are, for example, materials which upon exposure to alignment light induce anisotropy by photo-dimerization, photo-decomposition, trans-cis-isomerization, or photo-fries rearrangement. Preferred photoalignable materials are those in which upon exposure to aligning light an anisotropy is generated such that a slave material in contact with the photoalignable material may be oriented. Preferably, the above-mentioned slave material is a liquid crystal material, in particular an LCP-material.

Photoalignable materials, such as those described above, incorporate photoalignable moieties that are capable of developing preferential directions and thus anisotropic properties upon exposure to aligning light. The photo-alignable component preferably has anisotropic absorption properties. Typically, the above components exhibit absorption within the wavelength range of 230-. Preferably, the photoalignable component exhibits light absorption in the wavelength range 300-450nm, more preferably a component exhibiting absorption in the wavelength range 350-420 nm.

Preferably, the photoalignable moiety has a carbon-carbon, carbon-nitrogen, or nitrogen-nitrogen double bond.

For example, the photoalignable moiety is a substituted or unsubstituted azo dye, anthraquinone, coumarin, merocyanine (mericyanine), 2-phenylazothiazole, 2-phenylazobenzothiazole, stilbene, cyanostilbene, fluorostilbene, cinnamonitrile, chalcone, cinnamate, cyanocinnamate, stilbazolium (stilbazolium), 1, 4-bis (2-phenylvinyl) benzene, 4' -bis (arylazo) stilbene, perylene, 4, 8-diamino-1, 5-naphthoquinone dye, aryloxycarboxyl derivative, aryl ester, N-arylamide, polyimide, diarylketone having a ketone moiety or ketone derivative conjugated to two aromatic rings, such as substituted benzophenone, phenylhydrazone, and semicarbazone.

The preparation of the above listed anisotropic absorbent materials is well known as disclosed, for example, in U.S. Pat. No. 3,4,565,424 to Hoffman et al, U.S. Pat. No. 4,401,369 to Jones et al, Cole, U.S. Pat. No. 4,122,027 to Jr. et al, U.S. Pat. No. 4,667,020 to Etzbach et al, and U.S. Pat. No. 5,389,285 to Shannon et al.

Preferably, the photoalignable moiety comprises an arylazo compound, a poly (arylazo), a stilbene, a cyanostilbene, a cinnamate or a chalcone.

The photo-alignable material may be in the form of a monomer, oligomer or polymer. The photoalignable moieties may be covalently bonded within the backbone or covalently bonded within the polymer or oligomer side chains or they may be part of a monomer. The photoalignable material may also be a copolymer comprising different types of photoalignable moieties or it may be a copolymer comprising side chains with and without photoalignable moieties.

The polymer means, for example, polyacrylate, polymethacrylate, polyimide, polyurethane, polyamic acid, polymaleimide, poly-2-chloroacrylate, poly-2-phenylacrylate; unsubstituted or having C₁-C₆Alkyl-substituted polyacrylamides, polymethacrylamides, poly-2-chloroacrylamides, poly-2-phenylacrylamides, polyethers, polyvinyl ethers, polyesters, polyvinyl esters, polystyrene derivatives, polysiloxanes, linear or branched alkyl esters of polyacrylic or polymethacrylic acid; poly (phenoxyalkyl acrylates), poly (phenoxyalkyl methacrylates), poly (phenylalkyl-acrylates) having an alkyl residue of 1 to 20 carbon atoms; polyacrylonitrile, polymethacrylonitrile, cyclic olefin (cyclophilin) polymers, polystyrene, poly-4-methylstyrene or mixtures thereof.

The photoalignable material may also comprise sensitizers such as ketocoumarins and benzophenones.

Further, preferred photo-alignable monomers or oligomers or polymers are disclosed in U.S. patents nos. US5,539,074, US6,201,087, US6,107,427, US6,632,909 and US7,959,990.

Examples

Synthesis of photo-alignment polymers

Preparation of example A14,4, 4-Trifluorobutyl (E) -3- (4-hydroxyphenyl) prop-2-enoate

164.16g of p-coumaric acid was dissolved in 1000ml of N-methyl-2-pyrrolidone. 152.54g of 1, 8-diazabicyclo [5,4,0] undec-7-ene were added slowly, followed by 237.99g of 1,1, 1-trifluoro-4-iodobutane. The brownish solution is heated to 70 ℃ with stirring and left at this temperature for 2 h. HPLC analysis showed unreacted coumaric acid still present, an additional 47.60g of trifluoro-iodobutane was added and the reaction was continued for an additional 2h at 70 ℃.

The reaction mixture is then diluted with 5000ml of ethyl acetate and 5000ml of 5% aqueous hydrochloric acid are added. The biphasic mixture was stirred at room temperature for 10 minutes and the aqueous phase was removed. The organic phase is washed with 5000ml of 5% aqueous sodium bicarbonate solution and 5000ml of 10% aqueous sodium chloride solution. The remaining organic phase was diluted with 3000 ml of toluene and partially concentrated by distilling off the solvent under vacuum to leave 762 g of a brown liquid product containing some salt residue, which was removed by filtration. Further distillation afforded 437 grams of the crude liquid product. 400ml of heptane were slowly added at about 70 ℃ and the mixture was crystallized by cooling to room temperature and finally to 0 ℃. The crystalline precipitate was filtered off, washed with a toluene/heptane ═ 1/1(v/v) solvent mixture and dried under vacuum at 40 ℃ to constant weight.

231.7g of crystalline trifluorobutyl ester A1 were obtained with an HPLC purity of 99.71 area%.

Preparation of example A24,4, 4-Trifluorobutyl (E) -3- [4- (6-Hydroxyhexyloxy) phenyl]2-propenoic acid ester

231.00g of trifluorobutyl ester A1 were dissolved in 1100ml of dimethylformamide. 138.69g of 6-chloro-1-hexanol were added, followed by 151.98g of finely divided potassium carbonate and 14.04g of finely divided potassium iodide. The yellow-brown suspension was heated to 100 ℃ and stirred at this temperature for 3 h. HPLC analysis showed less than 0.5% residual a 1. The yellow suspension is cooled to room temperature, the solid salt is filtered off and the clear filtrate is diluted with 5000ml of ethyl acetate, washed with 5000ml of 5% aqueous hydrochloric acid and then with 5000ml of 5% aqueous sodium bicarbonate and finally with 5000ml of 10% aqueous sodium chloride. The organic phase was diluted with 2000ml of toluene and partially concentrated by distilling off the solvent under vacuum to afford a brown liquid product containing some salt residue, which was removed by filtration. Further distillation provided 500 g of a liquid crude product. 400ml of heptane were slowly added at about 70 ℃ and the mixture was crystallized by cooling to room temperature, yielding crystalline bodies. Cooling was continued to 0 ℃ and the crystalline precipitate was filtered off, washed with heptane and dried under vacuum at room temperature to constant weight.

283.6g of crystalline product A2 are obtained with an HPLC purity of 96% area.

Preparation of example A36- [4- [ (E) -3-oxo-3- (4,4, 4-trifluorobutoxy) prop-1-enyl]Phenoxy radical]Hexyl 2-methylpropyl-2-enoate

112.32g of product A2 were dissolved in 600ml of toluene. 12.09g of 4- (dimethylamino) pyridine are added, followed by 0.27g of 2, 6-di-tert-butyl-4-methylphenol and 36.16g of methacrylic acid. The resulting yellow solution was cooled to 0 ℃ and a solution of 86.66g of N, N' -dicyclohexylcarbodiimide in 100ml of toluene was added slowly. After stirring for 1h at 0-10 ℃, the cooling bath was removed and the reaction mixture was stirred at room temperature overnight.

The suspension is treated with 500ml of 5% aqueous sodium bicarbonate solution at room temperature for 30 minutes. The aqueous phase was removed. The organic phase is washed once with 200ml of 5% aqueous hydrochloric acid and once with 200ml of 10% aqueous sodium chloride. The organic phase is filtered and partially concentrated by distilling off the solvent under vacuum. The liquid residue is filtered off and the filtrate is further concentrated to a final volume of 200ml to 250 ml. 200ml of heptane were added and the mixture was cooled to about-10 ℃. The crystalline precipitate formed was isolated by filtration, washed with low temperature heptane and dried under vacuum at room temperature.

105.33g of crystalline monomer A3 were obtained with an HPLC purity of 97.3 area%.

Preparation of example A4Poly-6- [4- [ (E) -3-oxo-3- (4,4, 4-trifluorobutoxy) prop-1-enyl]Phenoxy radical]Hexyl-2-methylprop-2-enoate.

25.00g of monomer A3 were dissolved in 187ml of N-methyl-2-pyrrolidone. The nearly colorless solution was purged by cyclically applying vacuum followed by a nitrogen purge 5 times. The solution is then heated to 65. + -. 1 ℃ and when this temperature has been reached a solution of 0.125g of 2,2' -azobis (2-methylpropionitrile) in 19ml of N-methyl-2-pyrrolidone, purified in the same way and added. The polymerization was continued at 65. + -. 1 ℃ for 6 hours with stirring and then cooled to room temperature with stirring.

The solid polymer was isolated by dropping the polymer solution under vigorous stirring into 1500ml of cooled (-10 ℃) methanol. The precipitate was filtered off while still cooling and drying at vacuum chamber temperature.

Polymer a4 was obtained with Mw 92164 and Mn 26774.

Preparation of example A5Poly-6- [4- [ (E) -3-oxo-3- (4,4, 4-trifluorobutoxy) prop-1-enyl]Phenoxy radical]Hexyl 2-methylprop-2-enoate

25.00g of monomer A3 were dissolved in 234ml of toluene. The nearly colorless solution was purged by cyclically applying vacuum followed by a nitrogen purge 5 times. Heating to 65. + -. 1 ℃ and when this temperature is reached, 0.13g of 2,2' -azobis (2-methylpropanenitrile) in 26ml of toluene are purified in the same way and added. The polymerization was continued for 20 hours at an internal temperature of 65. + -. 1 ℃ with stirring. A second portion of 0.13g AIBN was dissolved in toluene, added and the temperature raised to 75 ℃. The polymerization was continued for a further 20 hours. A third portion of 0.13g AIBN was added and the polymerization was continued at 75 ℃ for 20 hours. A fourth portion of 0.13g AIBN was added and the polymerization was continued for 20 hours. The resulting polymer solution can be used as is or the solid polymer a5 can be isolated as a viscous resin by evaporation of the solvent, with Mw 19989 and Mn 11700.

Preparation of example A66- [4- [ (E) -3-oxo-3- (4,4, 4-trifluorobutoxy) prop-1-enyl]Phenoxy radical]Hexyl 2-methylprop-2-enoate and 6- [4- [ (E) -3-methoxy-3-oxo-prop-1-enyl]Phenoxy radical]Copolymers of hexyl 2-methylprop-2-enoic acid esters.

14.00g of monomer A3 and 11.00g of monomer 6- [4- [ (E) -3-methoxy-3-oxo-prop-1-enyl ] phenoxy ] hexyl 2-methylprop-2-enoate [439661-46-8] were dissolved in 187ml of N-methyl-2-pyrrolidone. The solution was purged by cycling 5 times to apply vacuum followed by a nitrogen purge. The solution is then heated to 65. + -. 1 ℃ and, when this temperature is reached, 0.127g of 2,2' -azobis (2-methylpropionitrile) in 19ml of N-methyl-2-pyrrolidone, purged in the same way and added. The polymerization was continued at 65 ± 1 ℃ internal temperature with stirring for 6 hours and then cooled to room temperature with stirring.

The solid polymer was isolated by dropping the polymer solution under vigorous stirring into 1500ml of cooled (-10 ℃) methanol. The precipitate was filtered off while still cooling at vacuum chamber temperature and the tough polymer dried.

Polymer a6 was obtained with Mw 88374 and Mn 35338.

Preparation of example A7(E) -3- (4-acetoxyphenyl) prop-2-enoic acid

164.16g of p-coumaric acid were dissolved in 500ml of pyridine and the solution was cooled to 10 ℃. 270g of acetic anhydride are added with stirring at 10-15 ℃ over 20 minutes. The reaction mixture was stirred at room temperature overnight. The clear, yellow-brown solution is slowly added to a mixture of 1000 grams of ice and 750ml of 25% hydrochloric acid. The resulting colorless suspension was stirred at room temperature for 2 h. The solid product was filtered off, washed thoroughly with a lot of water and dried under vacuum at 40 ℃ to constant weight. 204.4g of colorless, crystalline OH-protected coumaric acid A7 are obtained, having an HPLC purity of 95.2% by area. The product can be further purified by recrystallization from methyl ethyl ketone to an HPLC purity of 98.9% area.

Preparation of example A84,4,5,5, 5-Pentafluoropentyl (E) -3- (4-acetoxyphenyl) prop-2-enoate

A mixture of 51.55g of OH-protected coumaric acid A7, 53.40g of 4,4,5,5, 5-pentafluoropentanol and 2.50g of 4-dimethylaminopyridine in 300ml of dichloromethane was cooled to 0 ℃. A solution of 61.90g dicyclohexylcarbodiimide in 50ml dichloromethane was added with stirring at 0 ℃ over 15 minutes. The white suspension was stirred at 0 ℃ for a further 75 minutes and then at room temperature overnight. The solid DCC urea was filtered from the suspension and the filtrate was washed once with 200ml of 5% aqueous hydrochloric acid and twice with 200ml of 10% aqueous sodium chloride. The organic phase was dried again over sodium sulfate and the solvent was removed by distillation to give 90g of the OH-protected pentafluoropentyl ester A8 as a crystalline oil with an HPLC purity of 88.8% area. It was used directly in the next step.

Preparation of example A94,4,5,5, 5-Pentafluoropentyl (E) -3- (4-hydroxyphenyl) prop-2-enoate

89.98g of OH-protected pentafluoropentyl ester A8 were dissolved in 492ml of tetrahydrofuran. 49ml of methanol and 12.3ml of water were added to the solution, followed by 6.90g of pulverized potassium carbonate. The suspension was stirred and heated at 60 ℃ for 2.5 h. 800ml of ethyl acetate are added and the solution is washed with 300ml of 5% aqueous hydrochloric acid. The organic phase is washed twice with 300ml of 10% aqueous sodium chloride solution. After drying the organic phase over sodium sulfate and filtration, the solvent was distilled off to yield 80.5 g of pentafluoropentyl ester a9 (containing traces of solvent) as a crystalline oily product with an HPLC purity of 92.1% area. The product can be recrystallized in toluene/heptane to yield an HPLC purity of 94% area.

Preparation of example A104,4,5,5, 5-Pentafluoropentyl (E) -3- [4- (6-hydroxyhexyloxy) phenyl]2-propenoic acid ester

61.37g of pentafluoropentyl ester A9 were dissolved in 400ml of dimethylformamide. 31.03g of 6-chloro-1-hexanol were added, followed by 34.00g of finely divided potassium carbonate and 3.14g of finely divided potassium iodide. The yellow suspension was stirred and heated at 100 ℃ for 3 hours. The yellow suspension is cooled to room temperature, the solid salt is filtered off and the clear filtrate is slowly added at 5 ℃ to a mixture of 800ml of water and 200ml of 25% aqueous hydrochloric acid. The precipitated product was filtered off and the filter cake was washed thoroughly with water. It is dissolved in 500ml of ethyl acetate and the solution is washed with 300ml of a 5% aqueous sodium bicarbonate solution and then with 300ml of a 10% aqueous sodium chloride solution. After drying the organic phase over sodium sulfate, the filtered solution was evaporated to dryness to give 80g of hydroxyalkylated pentafluoropentyl ester a10 as an orange oil with HPLC purity 91.5% area, which crystallized on cooling. The product can be recrystallized in toluene/heptane to provide an improved HPLC purity of 94% area.

Preparation of example A116- [4- [ (E) -3-oxo-3- (4,4,5,5, 5-pentafluoropentyloxy) prop-1-enyl]Phenoxy radical]Hexyl 2-methylprop-2-enoate

56.15g of hydroxyalkylated pentafluoropentyl ester A10 were dissolved in 300ml of toluene. 13.67g of methacrylic acid, 1.29g of 4-dimethylaminopyridine and 0.13g of 2, 6-di-tert-butyl-4-methylphenol are added and brought into solution. After cooling to 0 ℃ a solution of 32.76g dicyclohexylcarbodiimide in 50ml toluene was added with stirring at 0 ℃ over 15 minutes. The white suspension was stirred at 0 ℃ for a further 75 minutes and then at room temperature overnight. 350ml of 5% aqueous sodium bicarbonate solution were added to the white suspension and stirring was continued for 1 h. The suspension was filtered, the filter cake (mainly DCC urea) was washed with toluene and the aqueous phase was separated. The organic phase is washed with 500ml of 5% aqueous hydrogen chloride solution and 500ml of 10% aqueous sodium chloride solution. After drying over sodium sulfate, the solution was evaporated to dryness to give 64.97 g of pentafluoropentyl methacrylate a11 as a slightly yellow crystalline oil. The crude product obtained is dissolved in 400ml of dichloromethane and filtered through a short column of 100 g of silica gel (pore size 60. ANG., 230-400 mesh sieve size). The filtrate was evaporated to dryness to give 55.85 g of colorless, crystalline pentafluoropentyl methacrylate A11 with an HPLC purity of 95.4 area%.

Preparation of example A12Poly-6- [4- [ (E) -3-oxo-3- (4,4,5,5, 5-pentafluoropentyloxy) prop-1-enyl]Phenoxy radical]Hexyl 2-methylprop-2-enoate

10.00g of monomer A11 were dissolved in 45ml of tetrahydrofuran. 0.05g of 2,2' -azobis (2-methylpropanenitrile) was added and the solution was purged by cycling 5 times to apply vacuum followed by a nitrogen purge. The solution was stirred at 60 ℃ under nitrogen for 60 h. The solid polymer was isolated by dropping the polymer solution into 500ml of cooled (-10 ℃) methanol under vigorous stirring. The precipitate was filtered off while still cooling and drying at vacuum chamber temperature.

Polymer A12 was obtained with a Mw of 211'546 and a Mn of 110' 369.

Preparation of example A13(3,4, 5-trifluorophenyl) methyl (E) -3- (4-hydroxyphenyl) prop-2-eneAcid esters

18.18g p-coumaric acid was dissolved in 110ml N-methyl-pyrrolidone. 16.90g of 1, 8-diazabicyclo [5,4,0] undec-7-ene are added dropwise, followed by 20.00g of 3,4, 5-trifluorobenzyl chloride. The light brown solution was stirred at 70 ℃ for 3h, cooled to room temperature and diluted with 500ml of ethyl acetate. It is extracted with 500ml of 5% aqueous hydrochloric acid, followed by extraction with 500ml of 5% aqueous sodium bicarbonate and 500ml of water. After drying over sodium sulfate, the solution was filtered and evaporated to dryness to yield 32.00 g of slightly light brown crystalline product. It was recrystallized from toluene to provide 27.02 g of colorless trifluorobenzyl ester A13, purity 97.7% area (HPLC).

Preparation of example A14(3,4, 5-trifluorophenyl) methyl (E) -3- [4- (6-hydroxyhexyloxy) phenyl]2-propenoic acid ester

29.00g of trifluorobenzyl ester A13 were dissolved in 140ml of dimethylformamide. 15.43g of 6-chloro-1-hexanol were added, followed by 16.91g of finely divided potassium carbonate and 1.56 g of finely divided potassium iodide. The yellow suspension was stirred and heated at 100 ℃ for 3 h. The yellow suspension is cooled to room temperature, the solid salt is filtered off and the clear filtrate is slowly added at 5 ℃ to a mixture of 800ml of water and 200ml of 25% aqueous hydrochloric acid. The precipitated product was filtered off and the filter cake was washed thoroughly with water. It is then dissolved in 400ml of ethyl acetate and the solution is washed with 400ml of a 5% aqueous sodium bicarbonate solution and then with 300ml of water. After drying the organic phase with sodium sulphate, the filtered solution was evaporated to dryness to yield 40.2g of a light brown oil. The resulting crude product was dissolved in toluene and crystallized by addition of heptane and cooled to afford 30.48g of colorless hydroxyalkylated coumarate a14 with an HPLC purity of 90.7% area.

Preparation of example A156- [4- [ (E) -3-oxo-3- [ (3,4, 5-trifluorophenyl) methoxy group]Prop-1-enyl]Phenoxy radical]Hexyl 2-methylprop-2-enoate

30.00g of hydroxyalkylated coumarate A14 were dissolved in 160ml of toluene. 8.85g of methacrylic acid, 2.96g of 4-dimethylaminopyridine and 0.07g of 2, 6-di-tert-butyl-4-methylphenol are added and introduced into the solution. After cooling to 0 ℃ a solution of 21.22g dicyclohexylcarbodiimide in 27ml toluene was added with stirring at 0 ℃ over 15 minutes. The white suspension was stirred at 0 ℃ for a further 75 minutes and then at room temperature overnight. 150ml of 5% aqueous sodium bicarbonate solution were added to the white suspension and stirring was continued for 1 h. The suspension was filtered, the filter cake (mainly DCC urea) was washed with toluene and the aqueous phase was separated. The organic phase is washed with 500ml of 5% aqueous hydrogen chloride solution and 500ml of 10% aqueous sodium chloride solution. After drying the organic phase with sodium sulphate, the filtered solution was evaporated to dryness to yield 38.37g of a light brown oil. The crude product obtained is dissolved in 800ml of dichloromethane and filtered through a short column of 200 g of silica gel (pore size 60. ANG., 230-400 mesh size). The filtrate was evaporated to dryness to give 26.27 g of colorless, crystalline trifluorobenzyl methacrylate a15 with HPLC purity 94.4% area. The product can be recrystallized in toluene/heptane to provide an improved HPLC purity of 97.3% area.

Preparation of example A16Poly-6- [4- [ (E) -3-oxo-3- [ (3,4, 5-trifluorophenyl) methoxy]Prop-1-enyl]Phenoxy radical]Hexyl 2-methylprop-2-enoate

8.40g of monomer A15 were dissolved in 38ml of tetrahydrofuran. 0.04g of 2,2' -azobis (2-methylpropanenitrile) was added and the solution was purged by cycling 5 times to apply vacuum followed by each nitrogen sweep. The solution was stirred at 60 ℃ under nitrogen for 18 h. The solid polymer was isolated by dropping the polymer solution under vigorous stirring into 500ml of cooled (-10 ℃) methanol. The precipitate was filtered off while still cooling under vacuum at 40 ℃ and dried. Polymer a16 was obtained with a Mw of 290'955 and a Mn of 48' 432.

Preparation of oriented object Material (OSM)

OSM 1

1.98g of polymethyl methacrylate (Fluka) with Mw 15000 are dissolved in 8.0g of toluene, followed by 0.02g of Polymer A4 to give OSM 1.

OSM 2

3.409g of polymethyl methacrylate (Fluka) with Mw 15000 were dissolved in 6.5g of toluene, followed by 0.091g of Polymer A4 to give OSM 2.

OSM 3

1.9g of polymethyl methacrylate (Fluka) with Mw 15000, followed by 0.1g of Polymer A4 were dissolved in 8.0g of toluene to give OSM 3.

OSM 4

3.325g of polymethyl methacrylate (Fluka) with Mw 15000, followed by 0.175g of Polymer A4 were dissolved in 6.5g of toluene to give OSM 4.

OSM 5

3.28g of CN9010EU (Sartomer), 3.28g of SR351(Sartomer) and 3.28g of Miramer M1183(Miwon Specialty Chemical) were mixed with stirring. 0.1g of Polymer A4 was added and the mixture was further stirred overnight. 0.1g cumene hydroperoxide (Aldrich) was added and the mixture was stirred for a further 1h to give OSM 5.

OSM 6

1.88g of CN9010EU (Sartomer), 3.76g of SR9035(Sartomer) and 3.76g of Miramer M1183(Miwon Specialty Chemical) were mixed with stirring. 0.5g of Polymer A4 was added and the mixture was further stirred overnight. 0.1g cumene hydroperoxide (Aldrich) was added and the mixture was stirred for a further 1h to give OSM 6.

OSM 7

4g of CN9010EU (Sartomer), 7.8g of SR9035(Sartomer) and 7.8g of Miramer M1183(Miwon Specialty Chemical) were mixed with stirring. 0.2g of Polymer A4 were added and the mixture was further stirred overnight. 0.2g of Irgacure 819(BASF) was added and the mixture was stirred for a further 1h to give OSM 7.

OSM 8

1.88g of CN9010EU (Sartomer), 3.76g of SR9035(Sartomer) and 3.76g of Miramer M1183(Miwon Specialty Chemical) were mixed with stirring. 0.5g of Polymer A5 was added and the mixture was further stirred overnight. 0.1g of Irgacure 819(BASF) was added and the mixture was stirred for a further 1h to give OSM 8.

OSM 9

1.88g of CN9010EU (Sartomer), 3.76g of SR9035(Sartomer) and 3.76g of Miramer M1183(Miwon Specialty Chemical) were mixed with stirring. 0.5g of Polymer A6 was added and the mixture was further stirred overnight. 0.1g of Irgacure 819(BASF) was added and the mixture was stirred for a further 1h to give OSM 9.

OSM 10

1.9g of polymethyl methacrylate (Fluka) with Mw 15000, followed by 0.1g of Polymer A12 were dissolved in 8.0g of toluene to give OSM 10.

OSM 11

1.9g of polymethyl methacrylate (Fluka) with Mw 15000, followed by 0.1g of Polymer A16 were dissolved in 8.0g of toluene to give OSM 11.

OSM 12

1.49g of cellulose acetate (Eastman CA-398-3) followed by 0.08g of Polymer A12 was dissolved in 8.43g of tetrahydrofuran to give OSM 12.

OSM 13

1.49g of cellulose acetate (Eastman CA-398-3) followed by 0.08g of Polymer A16 was dissolved in 8.43g of tetrahydrofuran to give OSM 13.

Preparation of polymerizable liquid Crystal Material (LCP)

LCP 1

1.9g of Paliocolor LC242(BASF) and 0.002g of 2, 6-di-tert-butyl-4-methylphenol (Fluka) were melted at 80 ℃. 0.098g of Irgacure 907(BASF) was added with stirring and mixed to give LCP 1.

LCP 2

1.9g of Paliocolor LC1057(BASF) and 0.002g of 2, 6-di-tert-butyl-4-methylphenol (Fluka) were melted at 105 ℃. 0.098g of Irgacure 907(BASF) was added with stirring and mixed to give LCP 2.

LCP 3

11.1g of benzoic acid, 2, 5-bis [ [4- [ [6- [ (1-oxo-2-propenyl) oxo ] hexyl ] oxo ] benzoyl ] oxy ] -, pentyl ester, 0.48g of Irgacure 907(BASF), 0.06g of TEGO Flow 300(Evonik), 0.012g of 2, 6-di-tert-butyl-4-methylphenol (Fluka) and 0.36g of Kayarad DPCA-20(Nippon Kayaku) were dissolved in 28.0 g of n-butyl acetate to give LCP 3.

Application examples

Application example 1

In this example a device was prepared as illustrated in fig. 3. OSM1 was coated on two glass plates 21, 25 as a support with a wire bar No.0(RK Print-Coat Instruments) and dried at 80 ℃ for 4 minutes, which produced an object in the form of a thin film with a thickness of 1 μm. The resulting objects 22 and 24 were then exposed to 200mJ/cm²(280-320nm) linearly polarized light, thereby defining the first and second alignment directions 27, 28, respectively. Two 40 μm thick tapes 26, 27 are placed on the coated side, close to the two parallel sides of the first glass as spacer. The first glass was then placed on a 60 ℃ hot plate. Preheated LCP 1(80 ℃) was dropped onto the first glass-coated side. A second glass is then placed with the coated side in contact with the LCP so that the alignment directions 27, 28 of the two photo-aligned objects are parallel. The device 20 thus assembled was heated at 80 ℃ for 10 minutes and then exposed to 2000mJ/cm²UV light (Fusion UV Systems, Bulb H) to cure the LCP. When the resulting device 20 is arranged between crossed polarizers, a uniform LCP orientation is observed along direction 29.

Application example 2

A device was prepared in the same manner as application example 1, except that OSM 3 was used instead of OSM 1. The film thickness of OSM1 was 0.8. mu.m. When the resulting device was placed between crossed polarizing prisms, uniform LCP orientation was observed.

Application example 3

OSM 2 was coated on top of two glass sheets as support with a Zehntner Coater (ZUA 2000.150 universal feeder) at 133 μm setting and dried at 80 ℃ for 4 minutes, which resulted in a film thickness of 16 μm. Using the two objects, a device was produced by the same method as in application example 1. When the resulting device was placed between crossed polarizing prisms, uniform LCP orientation was observed.

Application example 4

OSM 3 was coated onto both glass plates with a wire bar No.0(RK Print-Coat Instruments) and dried at 80 ℃ for 4 minutes as in application example 2. On top of the resulting OSM 3 layer 32 of the first coated glass plate 31, 0.5cm wide (80 μm) strips 34 made of cellulose triacetate film were placed in parallel, at a distance of 0.5cm, as illustrated in fig. 4 a. OSM 4 was coated with wire bar No.0 to make a film 33, still containing solvent (fig. 4 b). After the film was dried at 80 ℃ for 4 minutes, the strips 34 were removed to produce a structured surface with an area comprising only the film 32 and the film 33 (FIG. 4c) on top of the film 32, with an approximate thickness difference of 12 μm. The obtained object 35 is then exposed to (280-320nm),200mJ/cm²The linearly polarized light is thereby polarized in a direction parallel to the length direction of the structure, which corresponds to the length direction of the removed strips. Then, a device was prepared as in application example 1 using both glasses. When the acquisition device was arranged between crossed polarizers, a uniform LCP orientation was observed.

Application example 5

The device was prepared using OSM 3 as in application example 2, with the modification that LCP 2 was used instead of LCP 1, LCP 2 was preheated to 105 ℃ before dropping onto the object and the device was heated to 105 ℃ for 10 minutes before curing the LCP. When the resulting device was placed between crossed polarizing prisms, uniform orientation of the LCP layers was observed.

Application example 6

The same procedure as in application example 4 was used to prepare a device, with the modification that LCP 2 was used instead of LCP 1, LCP 2 was preheated to 105 ℃ before dropping onto the object and the device was heated to 105 ℃ for 10 minutes before curing the LCP. When the resulting device was placed between crossed polarizing prisms, uniform LCP orientation was observed.

Application example 7

OSM 5 was coated onto both glass sheets with a wire bar No.0(RK Print-Coat Instruments). The coating was cured first at 150 ℃ for 15 minutes and then at 200 ℃ for 10 minutes, resulting in a film thickness of 1 μm. Using the two objects, a device was produced by the same method as in application example 1. When the resulting device was placed between crossed polarizing prisms, uniform LCP orientation was observed.

Application example 8

OSM 5 was cast on top of a reflective aluminum foil and cured first at 150 ℃ for 15 minutes and then at 200 ℃ for 10 minutes, resulting in a film thickness of approximately 100 μm. The obtained object was then exposed to 200mJ/cm²(280-320nm) linearly polarized light. LCP 3 was spin coated at 2000rpm for 30 seconds and dried at 55 ℃ for 2 minutes. After cooling to room temperature, the LCP layer was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. When the LCP layer is viewed via a linear polarizer arranged above the LCP layer, a uniform orientation can be seen.

Application example 9

OSM 6 was coated onto a glass fiber board using a Zehntner Coater (ZUA 2000.150 universal feeder) at a 300 μm setting and cured at 150 ℃ for 30 minutes to produce a film having a thickness of 70 μm. The resulting photo-alignable object was then exposed to 500mJ/cm²(280-320nm) linearly polarized light. LCP 3 was spin coated on the object at 2000rpm for 30 seconds and dried at 55 ℃ for 4 minutes. After cooling to room temperature, the LCP layer was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. The film stack resulting from OSM 6 and LCP 3 coating is separated from the glass sheet. When the film was placed between crossed polarizing prisms, uniform LCP orientation was observed.

Application example 10

OSM 7 was coated on glass sheets with a 50 μm setting using a Zehntner Coater (ZUA 2000.150 universal feeder). After waiting 5 minutes at room temperature, the coating was left at 4000mJ/cm under nitrogen²(395nm) UV LED curing was performed to produce a film of 10 μm thickness. The resulting photo-alignable object was then exposed to 1000mJ/cm²(280-320nm) linearly polarized light. LCP 3 was spin coated at 2000rpm for 30 seconds and dried at 55 ℃ for 4 minutes. After cooling to room temperature, the LCP was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. When the coated glass sheet was observed between crossed polarizing prisms, uniform orientation was seen.

Application example 11

OSM 7 was coated on glass sheets with a 400 μm setting using a Zehntner Coater (ZUA 2000.150 universal feeder). After 5 minutes at room temperature, the resulting coating was 4000mJ/cm under nitrogen²(300-400nm) curing and a film thickness of about 220 μm. The obtained object was then exposed to 1000mJ/cm²(280-320nm) linearly polarized light. LCP 3 was spin coated at 2000rpm for 30 seconds and dried at 55 ℃ for 4 minutes. After cooling to room temperature, the LCP layer was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. When the coated glass sheet was observed between crossed polarizing prisms, uniform orientation was seen.

Application example 12

The stamping tool 40 is prepared from a first glass sheet 41 by affixing strips of tape 42 parallel to each other on the glass sheet, as illustrated in fig. 5 a. The distance between the strips was 0.5cm and the width of the strips was 1.8 cm. The tape thickness was 50 μm. The glass sheet with the adhesive strip was then treated with trichloro (1H, 2H-perfluorooctyl) silane vapor for 5 minutes, which was then the glass embossing tool 40. OSM 8 was coated on the second glass sheet 43 with a 200 μm setting using a Zehntner Coater (ZUA 2000.150 universal feeder) to produce a film 44. The glass embossing tool 40 is pressed onto the film 44, which is then passed at 4000mJ/cm²(395nm) UVLED ultraviolet radiation was irradiated through the glass embossing tool to cure. The glass stamping tool is then removed. Now on the second glass sheet 43 is a structured film 45 with two height faces 46 and 47 (fig. 5b), of which the lower height is about 60 μm and the upper height is about 105 μm. The photoalignable, structured object thus obtained is then exposedAt 1000mJ/cm²(280-320nm) linearly polarized light. LCP 3 was spin coated over the photo-aligned, structured object 45 at 2000rpm for 30 seconds and dried at 55 ℃ for 4 minutes. After cooling to room temperature, the LCP layer was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. When the device thus obtained is arranged between crossed polarizing prisms, a uniform orientation of the LCP layers is observed.

Application example 13

OSM 9 was preheated at 50 deg.C, filtered and coated onto glass sheets at a 50 μm setting with a Zehntner Coater (ZUA 2000.150 general feeder), then passed under nitrogen through a UVLED (395nm) at 4000mJ/cm²And (5) curing by light irradiation. Resulting in a film thickness of about 10 μm. The obtained object was then exposed to 1000mJ/cm²(280-320nm) linearly polarized light. LCP 3 was spin coated at 2000rpm for 30 seconds and dried at 55 ℃ for 4 minutes. After cooling to room temperature, the LCP was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. When the LCP layer was observed between crossed polarisers, uniform orientation was seen.

Application example 14

A device was prepared in the same manner as in application example 1, except that OSM10 was used instead of OSM1 and the resulting 1.3 μm thick film was exposed to 1000mJ/cm²(280-320nm) instead of 200mJ/cm²(280-320nm) linearly polarized light. When the resulting device was placed between crossed polarizing prisms, uniform LCP orientation was observed.

Application example 15

A device was prepared in the same manner as in application example 1, except that OSM 11 was used instead of OSM1 and the resulting 1.3 μm thick film was exposed to 1000mJ/cm²(280-320nm) instead of 200mJ/cm²(280-320nm) linearly polarized light. When the resulting device was placed between crossed polarizing prisms, uniform LCP orientation was observed.

Application example 16

OSM1 was prepared using a Zehntner Coater (ZUA 2000.150 general feeder) at a 100 μm setting2 are coated on a glass sheet. After 10 minutes at room temperature, the coating was dried at 70 ℃ for 10 minutes to give a dry film thickness of 13 μm. The obtained object was then exposed to 1000mJ/cm²(280-320nm) linearly polarized light. LCP 3 was spin coated at 2000rpm for 30 seconds and dried at 55 ℃ for 4 minutes. After cooling to room temperature, the LCP was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. When the LCP layer was observed between crossed polarisers, uniform orientation was seen.

Application example 17

A device was prepared in the same manner as in application example 16, but using OSM 13 instead of OSM 12. When the LCP layer was observed between crossed polarisers, uniform orientation was seen.

Application example 18

OSM 6 was coated on glass sheets with a 300 μm setting using a Zehntner Coater (ZUA 2000.150 universal feeder) and cured at 150 ℃ for 30 minutes to produce a film having a thickness of about 70 μm. The film is then removed from the substrate to obtain the photo-alignable object in the form of a free-standing film.

Application example 19

Application example 18 the free-standing film obtained was exposed to 500mJ/cm²(280-320nm) linearly polarized light. The photoalignment object in the form of a free-standing film was then mounted on a spin coater vacuum chuck and LCP 3 was spin coated on top of the photoalignment object at 2000rpm for 30 seconds and dried at 55 ℃ for 4 minutes. After cooling to room temperature, the LCP layer was at 1500mJ/cm under nitrogen²(300-400nm) UV curing. When the film was placed between crossed polarizing prisms, uniform LCP orientation was observed.